Open access peer-reviewed chapter

Determination of Concentration for Some Priority Substances in Paddy Fields of Ergene River, Meriç River, and Yenikarpuzlu Dam, Turkey

Written By

Barış Can Körükçü and Cemile Ozcan

Submitted: June 30th, 2020 Reviewed: July 15th, 2020 Published: September 1st, 2020

DOI: 10.5772/intechopen.93383

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Abstract

This study was intended in paddy (rice husk and rice), sediment, and irrigation water samples taken from the paddy fields of Ergene River, Meriç River, and Yenikarpuzlu Dam reservoir which are frequently grown in the river basin in Thrace region and endosulfan (EN) and PAHs were investigated. For analysis, EN and PAHs were studied by GC-MS. The data obtained as a result of the analyses were compared with the results of the standard reference items, and the accuracy of the results was determined. The standard addition method was used to prove the accuracy of EN and PAHs. The recovery parameters on the extraction efficiency of EN and PAHs were optimized, and the recoveries ranged from 82 to 105%. The methods showed good linearity for EN and PAHs, and the LOD and LOQ for methods were found 0.03–63.1 and 0.1–210 μg kg−1, respectively.

Keywords

  • Thrace region
  • paddy
  • sediment
  • water
  • endosulfan
  • PAHs

1. Introduction

Industrial and agricultural activities along with increasing industrialization are polluted very quickly of water and soil resources. When these sources of pollution are taken into consideration, it is necessary to follow the industrial and agricultural residues. These pollutants, which are used in agriculture and industry, interfere with the natural environment and threaten the ecological environment. Some pollutants can be found in the environment even after years of prohibition, and others can be transported over long distances. Pollutants are spread to the environment as industrial, agricultural and domestic sources [1, 2].

Direct transport of pesticides on the soil surface or on the plant play a role factors such as evaporation, surface flow, soil penetration and adsorption. Evaporation is on the soil, water and plant surface and the most important factor affecting the evaporation of pesticide is its evaporation pressure. In addition, high temperature, low relative humidity and air movement are environmental factors that accelerate evaporation. Pesticides strongly absorbed by soil particles are much less likely to evaporate [3, 4, 5].

Endosulfan (EN) is an organochlorine and acaricide group. Acute toxicity is a colorless, solid agricultural chemical prohibited due to its bioaccumulative potential and endocrine disrupting effects [4, 5, 6]. EN residues in nature are also known to remain in the soil for at least 6 years [7, 8]. Therefore, it requires examination of the soil contaminated with EN, the product grown in soil, sediment and the water used. Polycyclic systems occur when one ring is sharing two carbons with another ring, or the rings are connected to each other by a C▬C bond [9]. PAHs are from the group of compounds which show unsaturation in molecular formulas and do not give addition reactions which are characteristic for them. In the cyclic structure, PAHs from the class of planar molecules are resistant to oxidation. In addition, PAHs can be found in petrochemical, rubber, plastic, mineral oil, rust oil, paint, leather and other products. Rubber and plastic materials are high-risk materials containing PAH. In the Ergene Basin, where the industry is intense, these compounds are likely to be found. As the molecular weights of PAHs increase, their solubility in water decreases. However, their toxic and carcinogenic properties increase [9, 10, 11, 12]. Contaminated soil, air and aquatic products may also contain PAH. The cooking meat or other food on the grill or at high temperatures increases the amount of PAH in food [11]. In this study, analysis of EN and PAHs compounds shown in Figure 1 was performed.

Figure 1.

Structural formulas of analyzed compounds.

The organic components (PAHs and EN) we analyzed are considered among the primary pollutants [9, 13, 14, 15, 16, 17]. When the pesticides in our ecological environment are taken in high concentration, they can cause deformations on the biological structure of the organism. In the event of prolonged exposure to certain pesticides, cancer can be seen or short-term exposure may result in direct death [13, 15, 16, 17, 18, 19].

The extensively used high sensitivity analytical techniques for the determination of EN and PAHs at low concentrations in environmental samples are GC-MS [6, 8, 20, 21], HPLC-MS [10, 22]. The separation and preconcentration techniques for pesticides are solid phase extraction (SPE) [21, 23, 24], solid phase micro extraction (SPME) [21, 22, 25] and sonication [22, 26], which are used to solve these problems in analysis of EN and PAHs.

The aim of this study was intended in paddy (rice husk and rice), sediment, and irrigation water samples taken from the paddy fields of Ergene River, Meriç River, and Yenikarpuzlu Dam reservoir which are frequently grown in the river basin in Thrace region and EN and PAHs were investigated. Thrace region is a place where industry and agriculture are intense, so the analysis with real examples will be performed of great importance here. For this reason, EN and PAHs, which developed method validation, were studied by GC-MS.

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2. Materials and methods

Within the scope of this study, the paddy production areas in the agricultural areas of Thrace Region, direct irrigation from Ergene-Meriç rivers and dam ponds, Ergene and Meriç Basin were evaluated and three regions were determined as the study area. The sampling points are shown in Figure 2. Endosulfan and PAH analyses were made in paddy plant, sediment and irrigation water samples taken from paddy fields, which irrigated from the Ergene River, the Meriç River, and the Yenikarpuzlu Dam Reservoir, considering the distinction of irrigation resources in the rice plants often grown in river basins in the Thrace region. In the Yenikarpuzlu village of Edirne province, around Sığırcı Dam, and from the irrigated area from Edirne-İpsala-Yenikarpuzlu, Edirne-Merkez-Üyüklütatar and Edirne-Uzunköprü-Muhacirkadı Village were collected the paddy, sediment and paddy irrigation water (Figure 2). Endosulfan and PAH analysis were performed method validation by GC-MS.

Figure 2.

Representation of the sampling points on the map.

Agilent GC-MS was used in the determination phase for all studies. The instrument used is the HP-5 MS UI capillary column (30 m × 250μm × 0.25 μm) and the 5990C (Agilent) inert MSD mass detector with 7890A (Agilent) model GC-MS. The electron ionization (EI) system with 70 eV ionization energy in GC-MS, and the He gas was used as carrier gas.

2.1 Preparation of standard solutions

Dilution for Endosulfan (EN) was carried out on pure standard (SIGMA-ALDRICH, Product: 45852, EN solution 100 ng μL−1 in n-hexane, PESTANAL®). As a standard for PAHs, Dr. Ehrenstorfer 2095009 product PAH-mix 9 was used. In the standard, there are mixtures of 16 polycyclic aromatic hydrocarbons (PAHs); naphthalene (NAP), acenaphthalene (ACE), acenaphtylene (ACY), fluorene (FLU), phenantherene (PHN), anthracene (ANT), fluoranthene (FLR), pyrene (PYR), benz(a)anthracene (BaA), chrysene (CRY), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenz(a,h)anthracene (DahA), benzo(g,h,i)perylene (BghiP) and indeno(1,2,3,c,d)pyrene (IcdP). Optimum conditions of EN and PAHs were shown in Tables 1 and 2. According to the mass spectra of the chromatograms of the EN and PAH pesticides, column retention times and ion inputs were studied in SIM mode. Pesticide standards were prepared (0.1, 0.25, 0.5, 1, 2, 2.5, 5, 7.5, 10, 25, 50, 100, 250, 500, 750 and 1000 μg L−1) and measurements were taken. PAH-mix 9 of 16 polycyclic aromatic hydrocarbon compounds in standard contented NAP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF, BaP, DahA, BghiP and IcdP, and the dilution made out of from standard mixture was prepared standards of 1, 5, 10, and 25 μg L−1. The methods applied in GC–MS for EN and PAHs are given in Tables 1 and 2, respectively.

GC injection conditions
Applied methodSplitless
Injection volume1 μL
Temperature250°C
He gas flow rate1 mL/min
Total flow rate64 mL/min
Septum cleaning flow3 mL/min
Temperature program250°C for 1 min
Cleaning flow for split vent60 mL/min throughout 2.5 min
Transfer line temperature program150°C for 0 min, runtime 30 min
280°C for 0 min, runtime 30 min
Column oven temperature programMS information
Collection modeScan
Rate (°C/min)Temperature (°C)Standby time (min)Solvent delay (min)10.00
Gain factor5.00
45 (initial)1EM voltage obtained2271
211505MS source temperature (°C)230
42200MS Quad (°C)150
300 (post run)3Scanned mass range100–279

Table 1.

The optimum GC-MS conditions applied for endosulfan.

GC injection conditions
Applied methodSplitless
Injection volume1 μL
Inlet temperature70°C
He gas flow rate1 mL/min
Total flow rate64 mL/min
Septum cleaning flow3 mL/min
Temperature program300 °C for 1 min
Cleaning flow for split vent60 mL/min throughout 2.0 min
Transfer line temperature program150°C for 0 min, runtime 42.43 min
280°C for 0 min, runtime 41.43 min
Column oven temperature programMS information
Collection modeScan
Rate (°C/min)Temperature (°C)Standby time (min)Solvent delay (min)0.00
Gain factor5.00
70 (initial)1EM voltage obtained2329
101201MS source temperature (°C)230
727013MS Quad (°C)150
300 (post run)3Scanned mass range100–279

Table 2.

Optimum GC-MS conditions for PAHs.

The retention times (RT), SIM fragmentation ions, chromatogram programming times of PAHs are given in Table 3. The TICs of EN and PAHs were shown in Figures 3 and 4.

PesticidesRT (min)Target ionIon 1Ion 2Programming time (min)
Naphthalene (NAP)7.584128.00129.006.00
Acenaphthalene (ACE)12.394152.00153.008.00
Acenaphtylene (ACY)13.017153.00154.0012.67
Fluorene (FLU)14.694166.00165.0013.50
Phenantherene (PHN)17.846178.00176.00179.0015.00
Anthracene (ANT)17.994178.00176.00179.0017.91
Fluoranthene (FLR)21.850202.00200.00203.0018.10
Pyrene (PYR)22.556202.00200.00203.0022.15
Benz(a)anthracene (BaA)26.650228.00226.00229.0023.00
Chrysene (CRY)26.879228.00226.00229.0026.71
Benzo(b)fluoranthene (BbF)30.281252.00250.00253.0026.90
Benzo(k)fluoranthene (BkF)30.376252.00250.00253.0030.33
Benzo(a)pyrene (BaP)37.713252.00250.00253.0035.65
Benzo(g,h,i)perylene (BghiP)31.539276.00138.00277.0031.70
Dibenz(a,h)anthracene (DahA)38.082276.00278.00279.0037.95
Indeno(1,2,3,c,d)pyrene (IcdP)39.436276.00274.00277.0038.50

Table 3.

The retention times (RT), SIM fragmentation ions, and chromatogram programming times of PAHs.

Figure 3.

GC chromatograms of Endosulfan compound.

Figure 4.

GC chromatograms of PAH compounds.

The standards (EN and PAHs) were prepared in certain concentrations and readings were made in the device and the calibration graphs were plotted to calculate the amounts in the actual samples (Figures 5 and 6).

Figure 5.

The calibration graph of Endosulfan compound.

Figure 6.

The calibration graphs of PAHs compounds.

The linear regression, correlation coefficient, the detection limit (LOD) indicating the performance of the method in the method validation [14], the determination limit (LOQ), relative standard deviation percentage (RSD) and recovery calculations of the pesticides analyzed by GC-MS were shown in Table 4.

PesticidesRegression equation (linear range)R2LODLOQRSD%Recovery,%
1EN305.77x − 245.32 (1–1000 μg/kg)0.99990.792.647.39103
2NAP23,096x − 6571.3 (0.25–1000 μg/kg)0.99840.030.101.85105
3ACE16,398x − 91,561 (1–750 μg/kg)0.99890.230.761.1798.9
4ACY13,125x − 47,551 (0.5–750 μg/kg)0.99930.050.170.42101
5FLU11,643x − 78,796 (2.5–750 μg/kg)0.99850.431.461.6288.1
6PHN13,342x − 98,862 (2.5–750 μg/kg)0.99780.642.122.1796.5
7ANT6895.2x + 103,892 (2.5–750 μg/kg)0.99921.173.893.65100
8FLR9819.7x − 70,254 (2.5–750 μg/kg)0.99810.642.122.2891.6
9PYR9427.9x − 42,495 (2.5–750 μg/kg)0.99970.672.243.4297.6
10BaA821.31x − 1687.9 (25–750 μg/kg)0.99954.0513.524.9692.9
11CRY1401.4x − 36,903 (25–750 μg/kg)0.99856.7822.61.3586.9
12BbF512.66x − 20,563 (50–750 μg/kg)0.998612.340.94.8683.2
13BkF504.19x − 23,733 (50–750 μg/kg)0.997717.458.16.884.3
14BaP280.02x + 7583.6 (100–1000 μg/kg)0.999920.066.37.8782.5
15IcdP136.66x − 10,109 (250–1000 μg/kg)0.998163.12103.3386.1
16NAP127.67x − 7342 (250–1000 μg/kg)0.999142.21415.0590.2
17ACE214.46x − 8091.9 (50–1000 μg/kg)0.997414.046.75.7295.0

Table 4.

The values of linear regression (y = ax + b), correlation coefficient (R2), LOD (μg/kg), LOQ (μg/kg), and RSD% in the pesticides.

2.2 Collection of samples and preparation for analysis

For each point determined, twice samples were sampled in the months of July (sowing period) and September (harvesting period) in the periods of paddy sowing and harvesting. In the paddy pan, selected for sampling, three points were determined to represent each of the ceilings and pan water, soil and plant samples were made from these points. Since there were no paddy in the sowing period, only in the harvesting period of soil and water “at the latest 5 days before the harvest” were done every triple sampling. The pan water, sediment samples, rice grains and rice husk samples from the paddy samples were coded with the abbreviation “w,” “sd,” “r,” and “rh,” respectively. The coordinates of the locations, code and sampling dates are given in Table 5.

CoordinatesSowing periodHarvest period
CodeSampling dateWatering sourceCodeSampling dateWatering source
40°48′25.0″N 26°18′58.9″E1-w20.07.2016Dam Lake11-w22.09.2016Dam Lake
11-sd
1-sd11-r
11-rh
41°32′19.7″N 26°36′14.4″E2-w27.07.2016Meriç River22-w23.09.2016Meriç River
22-sd
2-sd22-r
22-rh
41°20′17.8″N 26°52′31.6″E3-w02.08.2016Ergene River33-w21.09.2016Ergene River
33-sd
3-sd33-r
33-rh

Table 5.

Sampling’s coordinates, codes, and dates.

Water samples prepared for analysis of EN and PAHs are enriched in the solid phase extraction system and prepared for analysis by GC-MS. Plant and sediment samples were enriched with modified QuEChERS method and prepared for analysis by GC-MS. The contents of the solid phase extraction and modified QuEChERS methods are given in Figure 7.

Figure 7.

The enrichment of samples with the solid phase extraction and modified QuEChERS methods.

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3. Results and discussion

Along with the developments in industrialization, it has made it necessary to determine organo-contaminant at major and minor levels in the settlements where there is a large amount of factories. In this study, The analysis of EN, NAP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF, BaP, DahA, BghiP and IcdP were performed in paddy, sediment and water samples taken during paddy planting and harvesting from the places such as Yeni Karpuzlu Dam, Muhacirkadı Village (Ergene River) and Üyüklütatar Village (Meriç River). These analyses were performed by using GC-MS. The results of the analysis of EN and PAHs in samples were given in Tables 68.

Sowing periodHarvest period
1Bsd11Bsd21Bsd311Bsd111Bsd211Bsd3
Dam BasinEN, mg/kg31.7 ± 1.728.0 ± 2.521.8 ± 2.617.5 ± 1.329.0 ± 2.322.5 ± 1.2
NAP, μg/kg385 ± 30376 ± 2325 ± 5306 ± 8307 ± 24314 ± 26
ACE, μg/kg61.8 ± 2.663.7 ± 5.662.5 ± 1.959.7 ± 4.154.7 ± 5.353.0 ± 4.6
ACY, μg/kg264 ± 1254 ± 14226 ± 9208 ± 7223 ± 10212 ± 16
FLU, μg/kg55.6 ± 1.570.5 ± 2.947.8 ± 2.845.1 ± 3.853.9 ± 1.366.7 ± 2.9
PHN, μg/kg318 ± 18263 ± 23164 ± 13124 ± 8113 ± 3120 ± 5
ANT, μg/kg485 ± 34383 ± 35197 ± 2122 ± 11102 ± 6115 ± 8
FLR, μg/kg273 ± 10247 ± 15236 ± 2201 ± 14204 ± 13204 ± 10
PYR, μg/kg1867 ± 1261617 ± 541622 ± 551265 ± 991245 ± 541291 ± 48
BaA, μg/kg708 ± 701231 ± 1101244 ± 95424 ± 42497 ± 36113 ± 7
CRY, μg/kg1058 ± 751190 ± 32NdNdNdNd
BbF, μg/kg970 ± 571775 ± 34Nd1293 ± 511074 ± 481118 ± 30
BkF, μg/kg1359 ± 1121436 ± 47900 ± 911354 ± 441124 ± 491163 ± 102
BaP, μg/kg2462 ± 1591768 ± 142478 ± 121383 ± 381737 ± 119312 ± 31
IcdP, μg/kg867 ± 3968 ± 59846 ± 42921 ± 19758 ± 53815 ± 58
Meriç-Üyüklütatar Village2Bsd12Bsd22Bsd322Bsd122Bsd222Bsd3
EN, mg/kg27.0 ± 1.724.2 ± 1.929.9 ± 2.436.9 ± 3.644.9 ± 2.739.7 ± 2.3
NAP, μg/kg336 ± 22278 ± 18321 ± 14296 ± 12311 ± 33254 ± 24
ACE, μg/kg64.1 ± 1.258.5 ± 4.658.5 ± 5.155.3 ± 4.954.6 ± 3.950.4 ± 3.1
ACY, μg/kg248 ± 17208 ± 16244 ± 10249 ± 28233 ± 5258 ± 15
FLU, μg/kg44.6 ± 4.444.0 ± 1.943.8 ± 3.450.3 ± 1.139.6 ± 3.938.9 ± 0.1
PHN, μg/kg104 ± 9126 ± 5104 ± 12108 ± 169.2 ± 6.177.4 ± 3.7
ANT, μg/kg85.5 ± 3.1127 ± 967.9 ± 5.293.7 ± 1.221.0 ± 1.336.3 ± 3.5
FLR, μg/kg212 ± 1212 ± 13196 ± 13182 ± 5156 ± 12149 ± 11
PYR, μg/kg1407 ± 611415 ± 1091328 ± 1071160 ± 17969 ± 92881 ± 71
BaA, μg/kg1115 ± 108519 ± 7341 ± 33749 ± 531093 ± 67154 ± 15
CRY, μg/kg1136 ± 120NdNdNd777 ± 69Nd
BbF, μg/kg1171 ± 1121084 ± 99885 ± 531122 ± 109753 ± 64661 ± 52
BkF, μg/kg1427 ± 1231011 ± 37368 ± 161391 ± 22801 ± 67Nd
BaP, μg/kg136 ± 17Nd310 ± 25160 ± 14NdNd
IcdP, μg/kg797 ± 36777 ± 49768 ± 95692 ± 8NdNd
IcdP, μg/kg797 ± 36777 ± 49768 ± 95692 ± 8NdNd
Muhacirkadı-Ergene Basin3Bsd13Bsd23Bsd333Bsd133Bsd233Bsd3
EN, mg/kg21.4 ± 2.223.0 ± 1.626.5 ± 1.933.7 ± 2.521.7 ± 2.323.3 ± 2.3
NAP, μg/kg322 ± 12417 ± 21408 ± 18219 ± 19242 ± 23226 ± 18
ACE, μg/kg56.5 ± 3.661.5 ± 1.256.8 ± 2.651.9 ± 2.044.1 ± 1.857.5 ± 3.4
ACY, μg/kg232 ± 18258 ± 12237 ± 7235 ± 14197 ± 19176 ± 16
FLU, μg/kg44.6 ± 0.748.6 ± 3.846.0 ± 1.4Nd62.4 ± 2.550.7 ± 4.1
PHN, μg/kg102 ± 6113 ± 577.8 ± 4.768.9 ± 6.466.7 ± 2.8101 ± 3
ANT, μg/kg81.7 ± 6.4103 ± 999.3 ± 2.520.3 ± 1.127.9 ± 2.179.6 ± 6.2
FLR, μg/kg190 ± 1137 ± 4196 ± 14137 ± 7245 ± 16179 ± 5
PYR, μg/kg1275 ± 721314 ± 621279 ± 90790 ± 781086 ± 471099 ± 52
BaA, μg/kg659 ± 66771 ± 781549 ± 143576 ± 41664 ± 55570 ± 50
CRY, μg/kgNdNd989 ± 91674 ± 32521 ± 23Nd
BbF, μg/kg1194 ± 281014 ± 591047 ± 96NdNd589 ± 36
BkF, μg/kg1243 ± 27580 ± 121098 ± 37Nd577 ± 32732 ± 33
BaP, μg/kgNdNdNd62.0 ± 6.2483 ± 38Nd
IcdP, μg/kg715 ± 28728 ± 32708 ± 24NdNdNd

Table 6.

Amount of pesticides in sediment samples in the dam basin, Meriç-Üyüklütatar village, and Muhacirkadı-Ergene Basin (n = 6).

Sowing PeriodHarvest Period
1Bw11Bw21Bw311Bw111Bw211Bw3
Dam BasinEN, mg/kgNdNdNdNdNdNd
NAP, μg/kg47.6 ± 4.447.3 ± 3.458.9 ± 2.970.1 ± 0.147.2 ± 3.2105 ± 9
ACE, μg/kg6.44 ± 0.0510.3 ± 0.6NdNdNdNd
ACY, μg/kg8.66 ± 0.878.76 ± 0.219.68 ± 0.4812.6 ± 0.710.3 ± 1.213.8 ± 1.1
FLU, μg/kg7.93 ± 0.786.73 ± 3.48.07 ± 0.276.76 ± 0.146.74 ± 0.377.70 ± 0.61
PHN, μg/kg60.6 ± 2.0104 ± 670.4 ± 2.244.8 ± 6.152.7 ± 1.953.8 ± 3.5
ANT, μg/kg91.6 ± 3.818.7 ± 0.7110 ± 462.0 ± 1.976.9 ± 3.679.0 ± 6.6
FLR, μg/kg18.2 ± 0.665.4 ± 4.218.3 ± 0.6316.2 ± 1.617.5 ± 0.616.5 ± 0.8
PYR, μg/kg66.6 ± 4.145.0 ± 3.462.0 ± 3.158.5 ± 0.365.8 ± 5.355.7 ± 4.2
BaA, μg/kg45.5 ± 2.363.9 ± 3.239.6 ± 3.034.9 ± 3.438.4 ± 3.330.5 ± 1.9
CRY, μg/kg62.0 ± 4.3NdNdNd60.8 ± 0.8Nd
Meriç-Üyüklütatar Village2Bw12Bw22Bw322Bw122Bw222Bw3
EN, mg/kg10.6 ± 0.3NdNdNdNdNd
NAP, μg/kg47.4 ± 1.153.7 ± 4.649.2 ± 2.539.5 ± 1.843.1 ± 2.241.1 ± 1.2
ACE, μg/kgNdNd6.60 ± 0.01NdNdNd
ACY, μg/kg8.86 ± 0.7110.1 ± 0.87.86 ± 0.519.97 ± 0.138.30 ± 0.309.10 ± 1.9
FLU, μg/kg7.24 ± 0.318.26 ± 0.477.58 ± 0.727.41 ± 0.426.84 ± 0.267.12 ± 0.59
PHN, μg/kg71.0 ± 2.579.1 ± 5.869.1 ± 1.162.1 ± 4.260.8 ± 6.361.4 ± 5.3
ANT, μg/kg111 ± 5126 ± 10108 ± 294.5 ± 7.992.0 ± 7.593.3 ± 3.8
FLR, μg/kg18.4 ± 0.620.4 ± 1.220.0 ± 1.417.2 ± 0.416.9 ± 0.617.3 ± 1.2
PYR, μg/kg61.8 ± 2.171.8 ± 3.275.7 ± 651.8 ± 3.750.8 ± 3.254.1 ± 3.8
BaA, μg/kg39.3 ± 0.444.7 ± 1.959.9 ± 4.127.4 ± 2.626.1 ± 2.129.7 ± 2.3
CRY, μg/kgNdNdNdNdNdNd
Muhacirkadı-Ergene Basin3Bw13Bw23Bw333Bw133Bw233Bw3
EN, mg/kg11.1 ± 0.67.36 ± 0.63Nd8.64 ± 0.327.85 ± 0.817.99 ± 0.46
NAP, μg/kg73.5 ± 2.153.0 ± 2.758.3 ± 3.942.4 ± 1.838.3 ± 1.146.7 ± 4.5
ACE, μg/kg6.82 ± 0.19NdNdNdNdNd
ACY, μg/kg14.8 ± 1.414.6 ± 0.6913.7 ± 1.312.7 ± 1.110.4 ± 0.812.8 ± 1.1
FLU, μg/kg10.6 ± 0.88.84 ± 0.129.09 ± 0.747.90 ± 0.587.41 ± 0.318.54 ± 0.52
PHN, μg/kg93.0 ± 1.483.3 ± 2.376.3 ± 6.276.3 ± 0.970.5 ± 6.188.4 ± 6.6
ANT, μg/kg152 ± 9134 ± 4121 ± 11121 ± 2110 ± 6144 ± 12
FLR, μg/kg24.2 ± 1.520.6 ± 0.819.0 ± 0.718.7 ± 0.217.5 ± 1.016.9 ± 0.1
PYR, μg/kg92.4 ± 1.672.8 ± 5.363.0 ± 5.161.7 ± 1.653.7 ± 4.248.7 ± 0.4
BaA, μg/kg88.3 ± 5.243.1 ± 4.143.3 ± 2.433.3 ± 2.530.6 ± 0.919.4 ± 0.0
CRY, μg/kg85.4 ± 2.4NdNdNdNdNd

Table 7.

Amount of pesticides in water samples in in the dam basin, Meriç-Üyüklütatar village, and Muhacirkadı-Ergene Basin (n = 6).

Rice Harvest PeriodRice Husk Harvest Period
Dam Basın11Br111Br211Br311Brh111Brh211Brh3
EN, mg/kg54.9 ± 4.646.4 ± 2.754.0 ± 2.847.4 ± 0.246.7 ± 1.641.6 ± 1.7
NAP, μg/kg220 ± 12265 ± 18280 ± 3679 ± 27420 ± 29327 ± 6
ACE, μg/kg58.3 ± 0.455.3 ± 0.965.1 ± 2.3246 ± 6265 ± 16239 ± 10
ACY, μg/kg205 ± 5246 ± 7216 ± 2444 ± 3374 ± 14341 ± 6
FLU, μg/kg71.9 ± 2.876.7 ± 2.399.0 ± 4.362.3 ± 0.459.1 ± 0.375.2 ± 0.1
PHN, μg/kg204 ± 4267 ± 7192 ± 1259 ± 18145 ± 2181 ± 10
ANT, μg/kg274 ± 7396 ± 14250 ± 2416 ± 32157 ± 9324 ± 7
FLR, μg/kg179 ± 3195 ± 1194 ± 4145 ± 4185 ± 4229 ± 2
PYR, μg/kg1068 ± 251148 ± 121142 ± 15779 ± 201080 ± 191351 ± 21
BaA, μg/kg1614 ± 371871 ± 861770 ± 631900 ± 1002100 ± 172760 ± 88
CRY, μg/kg1101 ± 221247 ± 591190 ± 301247 ± 591317 ± 181765 ± 58
BbF, μg/kgNd796 ± 79226 ± 25961 ± 91945 ± 931303 ± 20
BkF, μg/kgNdNd254 ± 24999 ± 991036 ± 1031253 ± 8
IcdP, μg/kg1044 ± 731101 ± 24843 ± 72076 ± 662134 ± 112343 ± 51
Meriç-Üyüklütatar Village22Br122Br222Br322Brh122Brh222Brh3
EN, mg/kg53.2 ± 1.460.1 ± 3.758.4 ± 1.643.4 ± 2.842.4 ± 3.541.8 ± 3.1
NAP, μg/kg239 ± 7356 ± 29383 ± 18809 ± 23628 ± 50882 ± 25
ACE, μg/kg63.4 ± 0.970.5 ± 0.960.3 ± 1.5179 ± 12150 ± 3153 ± 7
ACY, μg/kg194 ± 4242 ± 7275 ± 7403 ± 10401 ± 12382 ± 16
FLU, μg/kg73.7 ± 3.351.0 ± 1.5208 ± 15105 ± 492.5 ± 3.1102 ± 1
PHN, μg/kg79.3 ± 1.6139 ± 7428 ± 16179 ± 1193 ± 3254 ± 5
ANT, μg/kg39.6 ± 2.9172 ± 9338 ± 2652.1 ± 5.1235 ± 6402 ± 8
FLR, μg/kg195 ± 4213 ± 4228 ± 3239 ± 8297 ± 3270 ± 7
PYR, μg/kg1176 ± 191196 ± 161349 ± 181436 ± 401916 ± 331673 ± 48
BaA, μg/kg1120 ± 521478 ± 711831 ± 1012014 ± 793788 ± 1413909 ± 180
CRY, μg/kg829 ± 25969 ± 531225 ± 671330 ± 422375 ± 822400 ± 123
BbF, μg/kg215 ± 6202 ± 3617 ± 8950 ± 94294 ± 291261 ± 38
BkF, μg/kg245 ± 6261 ± 5270 ± 26918 ± 85537 ± 311120 ± 32
IcdP, μg/kg893 ± 6948 ± 241395 ± 552637 ± 801426 ± 212058 ± 75
Muhacirkadı-Ergene Basin33Br133Br233Br333Brh133Brh233Brh3
EN, mg/kg50.2 ± 2.117.7 ± 0.528.4 ± 1.545.6 ± 1.247.2 ± 1.641.6 ± 3.2
NAP, μg/kg285 ± 5445 ± 34514 ± 42603 ± 53524 ± 36517 ± 31
ACE, μg/kg77.0 ± 1.455.0 ± 0.259.9 ± 0.774.9 ± 2.794.4 ± 2.278.7 ± 4.0
ACY, μg/kg272 ± 8331 ± 7336 ± 23364 ± 19337 ± 9313 ± 12
FLU, μg/kg250 ± 14176 ± 4294 ± 16268 ± 25168 ± 13102 ± 3
PHN, μg/kg269 ± 22518 ± 9336 ± 30197 ± 4225 ± 5189 ± 3
ANT, μg/kg392 ± 33859 ± 18519 ± 15216 ± 2199 ± 3205 ± 8
FLR, μg/kg222 ± 6191 ± 4125 ± 6358 ± 8378 ± 7358 ± 9
PYR, μg/kg1202 ± 301078 ± 32789 ± 22293 ± 362576 ± 432336 ± 55
BaA, μg/kg1717 ± 61560 ± 67895 ± 612415 ± 463766 ± 1634258 ± 169
CRY, μg/kg1152 ± 101077 ± 37752 ± 51526 ± 442413 ± 1092562 ± 52
BbF, μg/kg901 ± 751029 ± 571255 ± 1151256 ± 1271042 ± 221220 ± 37
BkF, μg/kg949 ± 481403 ± 105599 ± 221722 ± 1341061 ± 31929 ± 35
IcdP, μg/kg1397 ± 241531 ± 231392 ± 412332 ± 962300 ± 221988 ± 52

Table 8.

The amounts of pesticides in the samples of rice and rice husk in the dam basin, Meriç-Üyüklütatar village and Muhacirkadı-Ergene Basin (n = 6).

Large scale accumulation or pollution of pesticide chemicals or natural chemicals is a source of concern for our global world. Due to the incorporation of these substances into the condensation and evaporation cycle, our natural life creates constant exposure with rain, snow and fog [26]. Soil pollution is closely related to industrial activities, destruction of municipal and industrial waste or environmental accidents. Soil is a complex and heterogeneous matrix with a porous structure containing inorganic and natural organic components [1, 2].

PAH components, which come out from the chemical production factories and vehicles’ exhausts along the Ergene River, constitute a serious source of pollution. In the Ergene Basin is located in petrochemical, rubber, plastic, mineral oil, rust oil, paint, leather and other products. Rubber and plastic materials including PAHs are high-risk materials. For this reason, EN and PAHs analyses of the samples collected from rice cultivated areas in the basin selected as clean region (Yeni Karpuzlu Dam), dirty region (Muhacirkadı Village) and less dirty region (Üyüklütatar Village) were determined. As the molecular weights of PAHs increase, their solubility in water decreases and accumulation in the sediment also increases. When the results obtained are examined, it can be seen that PAHs accumulate in the sediment.

Sampling during the sowing period and harvest period were made classifications as for proximity to the road, and irrigation channel, or proximity to the dam with code of 1B-1 and 11B-1, intermediate zones of 1B-2 and 11B-2, and the more distant area of 1B-3 and 11B-3.

The recoveries for EN and PAHs were ranged from 82.5 to 105%, respectively. The LOD and LOQ for EN and PAHs were found 0.03–63.1 and 0.1–210 μg kg−1, respectively.

The amount of EN, NP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF, BaP and IcdP in sediment samples were found to be 17.5–44.9 mg kg−1, 219–417 μg kg−1, 41.1–64.1 μg kg−1, 176–264 μg kg−1, Nd–70.5 μg kg−1, 66.7–318 μg kg−1, 20.3–485 μg kg−1, 137–273 μg kg−1, 790–1867 μg kg−1, 113–1549 μg kg−1, Nd–1190 μg kg−1, Nd–1775 μg kg−1g, Nd–1436 μg kg−1, Nd–2478 μg kg−1 and Nd–968 μg kg−1, respectively. The pesticide concentrations of BghiP and DahA in sediment samples were found below the limit of determination.

The amount of EN, NP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, and CRY in water samples were found to be Nd–11.1 mg L−1, 38.3–105 μg L−1, Nd–10.3 μg L−1, 8.30–14.8 μg L−1, 6.73–10.6 μg L−1, 44.8–104 μg L−1, 18.7–152 μg L−1, 16.2–65.4 μg L−1, 45.0–92.4 μg L−1, 19.4–88.3 μg L−1and Nd–85.4 μg L−1, respectively. The sample chromatograms of EN and PAHs in sediment, water, rice and rice husk are shown in Figures 8 and 9. Except for the clean area, EN was determined above the limit of detection in other sampling areas. The amount of EN in the dirty area was determined as ND-11.1 μg L−1. In the Harvest period for the polluted region were found 7.85, 7.99, and 8.64 μg L−1, respectively.

Figure 8.

Endosulfan chromatograms of samples taken from the paddy grown area.

Figure 9.

PAH chromatogram of samples taken from the paddy grown area.

Pesticides strongly absorbed by soil particles are much less likely to evaporate [1, 2, 24]. Since pesticides are more adsorbed in sediment samples, their transition to water decreases. The results were confirmed this. Sodium was found in higher concentrations than sediment samples because of its high solubility in water. This increases the electrical conductivity and reduces the water quality.

The amount of EN, NP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF and IcdP in rice samples were found to be 17.7–60.1 mg kg−1, 220–514 μg kg−1, 55.0–77.0 μg kg−1, 194–336 μg kg−1, 51.0–294 μg kg−1, 79.3–518 μg kg−1, 39.6–859 μg kg−1, 125–228 μg kg−1, 798–1349 μg kg−1, 895–1871 μg kg−1, 752–1247 μg kg−1, Nd–1255 μg kg−1, Nd–1403 μg kg−1 and 843–1531 μg kg−1, respectively. The pesticide concentrations of BaP, BghiP, DahA in rice samples were found below the limit of determination. The amount of PAHs in the polluted region was more than twice that of the clean region.

The amount of EN, NAP, ACE, ACY, FLU, PHN, ANT, FLR, PYR, BaA, CRY, BbF, BkF and IcdP in the rice husk samples were found to be 41.6–46.7 mg kg−1, 327–882 μg kg−1, 74.9–265 μg kg−1, 313–444 μg kg−1, 59.1–268 μg kg−1, 145–259 μg kg−1, 52.1–416 μg kg−1, 145–378 μg kg−1, 779–2576 μg kg−1, 1900–4258 μg kg−1, 1247–2562 μg kg−1, 294–1303 μg kg−1, 537–1722 μg kg−1 and 1426–2343 μg kg−1, respectively.

The amount of PAHs in the rice husk samples was found twice the amount of rice. Except for rice and water samples, PAHs accumulation was determined in sediment and rice husk samples.

If we summarize briefly, the BghiP and DahA pesticides in the sediment samples in Dam Basin, Meriç-Üyüklütatar Village and the Muhacirkadı-Ergene Basin was be bellowed of limit of detection. It was below the limit of detection of BbF, BkF, BaP, BghiP, DahA and IcdP pesticides content in water samples in the Dam Basin, Meriç-Üyüklütatar Village and the Muhacirkadı-Ergene Basin. It was below the limit of detection the BaP, BghiP and DahA pesticides in the rice and rice husk samples in the Dam Basin, Meriç-Üyüklütatar Village and the Muhacirkadı-Ergene Basin.

When the results were examined, it was determined that the amounts of pesticides were higher in the samples taken near the Ergene river, but the amounts in the edible section were less than in the rice husk. Rice husk has shown a very good adsorbent and reduced the transport of EN and PAHs in of food. EN and PAHs levels in samples taken from river, stream, or near the canal were found to be higher than the samples taken from the inner sides.

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4. Conclusion

Ergene River Basin surroundings were selected for this study: one heavily contaminated sites, moderately contaminated sites, and one less contaminated reference sites. The modified QuEChERS method used in this study was practical for mixtures found in environmental samples. This technique performs well, exhibiting good sensitivity, selectivity, and precision in the range of concentrations appropriate for the determination of target analytes. Our study investigated to the Ergene River Basin in sediment, rice, rice husk and water were analyzed for trace organic pollutants. However, the sediment and plant (rice and husk) had measurable and sometimes high levels of PAHs, even though no industrial sources of pollution were known. Other sources of PAH contamination may include runoff from paved roads and exhaust from farm machinery, and factory wastes immediate of the sampling stations. Therefore, in the alives feeding with husk of rice, there may be bioaccumulation of EN and PAHs. Ecological risk assessments for the sediment efficacies concluded that response actions were necessary for the sediment and husk, except for water and rice.

References

  1. 1. Bailey GW, White JL. Review of adsorption and desorption of organic pesticides by soil colloids, with implications concerning pesticide bioactivity. Journal of Agricultural and Food Chemistry. 1984;12:324-332. Available from:https://pubs.acs.org/doi/pdf/10.1021/jf60134a007?src=recsys
  2. 2. Soares AA, Albergaria JT, Domingues VF, Alvim-Ferraz MDCM, Delerue-Matos C. Remediation of soils combining soil vapor extraction and bioremediation: Benzene. Chemosphere. 2010;80:823-828. DOI: 10.1016/j.chemosphere.2010.06.036
  3. 3. Kurutaş E, Kılınç M. Pestisitlerin Biyolojik Sistemler Üzerine Etkisi. Arşiv Kaynak Tarama Dergisi. 2003;12:215-228. Available from:http://dergipark.org.tr/aktd/issue/2231/29481
  4. 4. Monneret C. What is an endocrine disruptor. Comptes Rendus Biologies. 2017;340:403-405. DOI: 10.1016/j.crvi.2017.07.004
  5. 5. Kabir ER, Rahman MS, Rahman I. A review on endocrine disruptors and their possible impacts on human health. Environmental Toxicology and Pharmacology. 2015;40:241-258. DOI: 10.1016/j.etap.2015.06.009
  6. 6. Chormey DS, Büyükpınar Ç, Turak F, Komesli OT, Bakırdere S. Simultaneous determination of selected hormones, endocrine disrupt or compounds, and pesticides in water medium at trace levels by GC-MS after dispersive liquid-liquid microextraction. Environmental Monitoring and Assessment. 2017;189:277-287. DOI: 10.1007/s10661-017-6003-6
  7. 7. Zhao C, Xie H, Mu Y, Xu X, Zhang J, Liu C, et al. Bioremediation of endosulfan in laboratory-scale constructed wetlands: Effect of bioaugmentation and biostimulation. Environmental Science and Pollution Research. 2014;21:12827-12835. DOI: 10.1007/s11356-014-3107-1
  8. 8. Kaur R, Rani S, Malik AK, Aulakh JS. Determination of endosulfan isomers and their metabolites in tap water and commercial samples using microextraction by packed sorbent and GC-MS. Journal of Separation Science. 2014;37:966-973. DOI: 10.1002/jssc.201301154
  9. 9. ATSDR. Agency for Toxic Substances and Disease Registry (ATSDR), Toxicological Profile for Polycyclic Aromatic Hydrocarbons (PAHs). Atlanta (GA): Department of Health and Human Services, Public Health Service, USA; 1995
  10. 10. Danyi S, Bose F, Brasseur C, Schneider YJ, Larondelle Y, Pussemier L. Analysis of EU priority polycyclic aromatic hydrocarbons in food supplements using high performance liquid chromatography coupled to an ultraviolet, diode array or fluorescence detector. Analytica Chimica Acta. 2009;633:293-699. DOI: 10.1016/j.aca.2008.11.049
  11. 11. Shi L, Zheng L, Liu R, Chang M, Huang J, Jin Q , et al. Quantification of polycyclic aromatic hydrocarbons and phthalic acid esters in deodorizer distillates obtained from soybean, rapeseed, corn and rice bran oils. Food Chemistry. 2019;275:206-213. DOI: 10.1016/j.foodchem.2018.09.119
  12. 12. Ferrarese E, Andreottola G, Oprea IA. Remediation of PAH contaminated sediments by chemical oxidation. Journal of Hazardous Materials. 2008;152:128-139. DOI: 10.1016/j.jhazmat.2007.06.080
  13. 13. EC. Priorty Substances and Certain Other Pollutions According to Annex II of Directing, 2008/105/EC. 2013. Available from:http://ec..europe.eu/enviromental/water/waterframework/priortysubstances.htm;eylul2013
  14. 14. US. US Food and Drug Administration, Guidance for Industry: Bioanalytical Method Validation. 2018. Available from:https://www.fda.gov/files/drugs/published/Bioanalytical-Method-Validation-Guidance-for-Industry.pdf
  15. 15. WHO. Application of Risk Analysis to Food Standards Issues, Report of the Joint FAO/WHO Expert Consultation, WHO/FNU/FOS/95.3. Geneva, Switzerland: World Health Organization; 1995
  16. 16. WHO. Guidelines for Assessing Quality of Herbal Medicines with Reference to Contaminants and Residues. Switzerland: World Health Organization; 2007. ISBN: 978 92 4 159444 8
  17. 17. Lepom P, Brown B, Hanke G, Lous R, Quevauviller P, Wollgast J. Needs for reliable analytical methods for monitoringe chemical pollutants in surface water under the European Water Framework Directive. Journal of Chromatography. A. 2009;1216:302-305. DOI: 10.1016/j.chroma.2008.06.017
  18. 18. WHO. Guidelines for Predicting Dietary Intake of Pesticide Residues (Revised), WHO/FSF/FOS/97.7. Geneva, Switzerland: World Health Organization; 1997
  19. 19. Casida JE, Durkin KA. Pesticide chemical research in toxicology: Lessons from nature. Chemical Research in Toxicology. 2017;30(1):94-104. DOI: 10.1021/acs.chemrestox.6b00303
  20. 20. Bulgurcuoğlu AE, Yılmaz B, Chormey DS, Bakırdere S. Simultaneous determination of estrone and selected pesticides in water medium by GC-MS after multivariate optimization of microextraction strategy. Environmental Monitoring and Assessment. 2018;190(4):252. DOI: 10.1007/s10661-018-6625-3
  21. 21. Bonansea RI, Amé MV, Wunderlin DA. Determination of priority pesticides in riverr water samples combining SPE and SPME coupled to GC-MS. Chemosphere. 2013;90:1860-1869. DOI: 10.1016/j.chemosphere.2012.10.007
  22. 22. Akvan N, Azimi G, Parastar H. Chemometric assisted determination of 16 PAHs in water samples by ultrasonic assisted emulsification microextraction followed by fast high-performance liquid chromatography with diode array detector. Microchemical Journal. 2019;150:104056. DOI: 10.1016/j.microc.2019.104056
  23. 23. Schenck FJ, Lehotay SJ, Vega V. Comparison of solid-phase extraction sorbents for cleanup in pesticide residue analysis of fresh fruits and vegetables. Journal of Separation Science. 2002;25:883-890. DOI: 10.1002/1615-9314(20021001)25:14<883::AID-JSSC883>3.0.CO;2-7
  24. 24. Correia-Sa L, Fernandes VC, Carvalho M, Calhau C, Domingues VF, Delerue-Matos C. Optimization of QuEChERS method for the analysis of organochlorine pesticides in soils with diverse organic matter. Journal of Separation Science. 2012;35:1521-1530. DOI: 10.1002/jssc.201200087
  25. 25. Kin CM, Huat TG, Kumari A. Application of solid-phase microextraction for the determination of pesticides in vegetable samples by gas chromatography with an electron capture detector. Malaysian Journal of Analytical Sciences. 2008;12:1-9. Avaialble from:http://www.ukm.my/mjas/v12_n1/1.pdf
  26. 26. Sheil D. Forests, atmospheric water and an uncertain future: The new biology of the global water cycle. Forest Ecosystems. 2018;5:19. DOI: 10.1186/s40663-018-0138-y

Written By

Barış Can Körükçü and Cemile Ozcan

Submitted: June 30th, 2020 Reviewed: July 15th, 2020 Published: September 1st, 2020